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Tribology International
journal homepage: www.elsevier.com/locate/triboint
School of Engineering and Technology, China University of Geosciences, Beijing 100083, China
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
c
School of Material Science & Engineering, Beijing Institute of Technology, Beijing 100081, China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 November 2011
Received in revised form
7 March 2012
Accepted 4 April 2012
Available online 13 April 2012
Keywords:
Sulfur- and phosphorus-free
Organomolybdenum additive
Lubrication
Tribological behavior
Introduction
It is well known that the addition of an appropriate additive to
an oil-based lubricant can effectively increase the mechanical
efciency, decrease the energy consumption, and reduce friction
and wear of machinery equipment. And more importantly, with
the consideration of environment and peoples health, to reduce
or eliminate some harmful elements like phosphorus, sulfur and
ash in the lubrication additives is an urgent direction of developing environment-friendly and efcient additives [14]. Moreover,
it is believed that sulfur and phosphorus (SP) oxides and metallic
ash formed in the engine oil can reduce catalyst effectiveness and
block lters, thereby degrading the exhaust after-treatment
system during extended engine operation. Because of this, the
International Lubricant Standardization and Approval Committee
(ILSAC) proposed the GF-4 Performance Standards to limit the
concentrations of phosphorus (0.08% maximum) and sulfur (0.50%
maximum) in the nished passenger car engine oil [5,6].
The additive zinc dialkyl dithiophosphate (ZDDP), a typical
additive containing sulfur, phosphorus and zinc, is used almost
universally in engine oils as an anti-oxidant and anti-wear agent.
It can form a glassy phosphate lm on the surface of Fe-based
materials to reduce wear and friction [710]. Another kind of
widely used additive is molybdenum dialkyldithiocarbamate
0301-679X/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.triboint.2012.04.002
Experimental details
Preparation of the N, N-bis (2-hydroxyethyl)-dodecanamide
molybdate (NNDM)
AR grade chemicals (dodecanoic acid, chlorine sulde, dichloromethane, diethanolamine, molybdenum trioxide) were used
for the synthesis of N, N-bis (2-hydroxyethyl)-dodecanamide
molybdate (NNDM). The synthetic routine is shown in Scheme 1,
containing three steps. Progress of all the reactions was monitored
by thin-layer chromatography (TLC), using CCl4Et2O (4:1) as eluent
and GC. In step (1), 0.1 mol dodecanoic acid was put into a 250 ml
151
152
ZDDP
MoDTC
NNDM
Mo
10
10
14
15
11
9.0
80
Transmittance (%)
100
8.5
60
40
20
8.0
0
2
3
Concentration (wt. %)
0
4000
3500
3000
2500
2000
1500
Wavenumber (cm-1)
1000
500
153
1000
NNDM
ZDDP
MoDTC
900
PB (N)
800
700
600
500
400
0.0
0.5
1.0
1.5
2.0
Concentration (%)
2.5
3.0
0.13
100
90
TG (%)
80
70
60
50
40
NNDM
ZDDP
MoDTC
0.12
295C
0.11
0.10
0.09
0.08
0.07
30
0.06
0.0
20
50
100 150 200 250 300 350 400 450 500 550 600
Temperature (C)
Fig. 4. TGA curve of NNDM.
0.5
1.0
1.5
2.0
Concentration (%)
2.5
3.0
154
than that of base oil 150SN (0.124). It indicated that NNDM had
excellent friction-reducing property.
Fig. 7 exhibits the variations of the worn scar diameters with
different concentrations of additives. It can be found that the
WSDs of all additives decreased with the increasing dosage, and
the WSDs lubricated by 150SN containing NNDM were always
smaller than those lubricated by 150SN containing ZDDP or
MoDTC. When the concentration was 3.0%, the WSD lubricated
by 150SN containing NNDM reached the minimum (about
0.43 mm), which was nearly half of that lubricated by base oil
150SN. It seemed that NNDM had better anti-wear behavior than
ZDDP and MoDTC under all the tested concentrations. It also
meant that the tribolm NNDM formed on the worn surface
exhibited a notable wear-resistance behavior.
0.9
NNDM
ZDDP
MoDTC
WSD (mm)
0.8
0.7
0.6
0.5
0.4
0.0
0.5
1.0
1.5
2.0
Concentration (%)
2.5
3.0
Fig. 8. SEM morphologies of the worn surfaces lubricated by different lubricants (392 N, 60 min): (a) 150SN; (b) 3.0% ZDDP 150SN; (c) 3.0% MoDTC 150SN;
(d) 3.0% NNDM 150SN.
EDS (at. %)
C
150SN
25.32
150SN 3% ZDDP
60.43
150SN 3% MoDTC 29.03
150SN 3% NNDM 31.46
Cr
Fe
Mo
Zn
3.60
9.19
8.15
3.51
0.77
1.25
0.53
0.60
0.88
69.83
26.25
61.57
61.90
0.55
1.48
1.33
0.47
0.10
1.8
155
Fig. 9. EDS spectra of worn surfaces lubricated by (a) 150SN; (b)3.0% ZDDP 150 SN; (c)3.0% MoDTC 150 SN; (d)3.0% NNDM 150 SN ( 392 N, 60 min ).
156
C 1s
284.6
Mo 3p
organic N1s
N 1s
(b)
Intensity
Intensity
(b)
(a)
Organic C
(a)
392
394
396
398
400
Binding Energy (eV)
FeO 2p3/2
Fe3O4 2p3/2
O 1s
402
404
Fe 2p
MoOx
Intensity
Intensity
(b)
(b)
Fe2O3 2p3/2
Fe-C
(a)
(a)
526
528
530
532
534
Binding Energy (eV)
536
MoO3 3d5/2
Mo 3d
Intensity
MoO3 3d3/2
(b)
MoO2 3d5/2
(a)
226 228 230 232 234 236 238 240 242 244
Binding Energy (eV)
Fig. 10. XPS spectra of C1s, N1s, O1s, Fe 2p and Mo 3d on the original worn surface (a) and the worn surface after 1 min sputtering and (b) lubricated by 3.0% NNDM.
Table 3
XPS quantication (at. %) of tribolm formed on the worn scar.
Elements
63.72
51.23
17.74
22.62
N (Mo)
5.15
1.13
Fe
Mo
2.98
13.95
10.41
11.07
Discussion
From the variations of tribological curves versus NNDM concentration (Figs. 6 and 7), it could be understood that the additive
NNDM without SP showed better friction-reducing behavior than
the additive ZDDP with SP, and especially showed better antiwear property than the additives ZDDP with SP and MoDTC with
S. When the concentration of NNDM reached 3.0%, friction
coefcient and wear scar diameter were 0.066 and 0.43 mm
respectively, which were smaller than those obtained from the
tests running on the base oil 150SN, 150SN containing ZDDP and
150SN containing MoDTC.
In the boundary lubrication regime, the formation of an adsorption layer or the production of a surface chemical reaction lm is the
determining factor in minimizing friction and wear [37]. The XPS
analysis results of the tribolm formed by 150SN containing NNDM
(Fig. 10 and Table 3) demonstrated that under the boundary
lubrication, the additive NNDM rst adsorbed on the metal surface,
and then decomposed and reacted with metal surface during the
rubbing process to form a stable tribolm on the rubbing surface.
This tribolm was composed of a reaction layer and an adsorption
layer. Therein, the reaction layer originated from the tribochemical
reactions of Mo element and O element in NNDM, while the
adsorption layer was formed by the coordination of long-chain
alkylamide with the metal surface. And two O atoms in the ring of
NNDM molecule structure, possessing two pairs of lone electrons
respectively, had strong electroafnity [31], which was endowed
NNDM with the strong coordinate capacity with metal ions or metal
surface, which was helpful to enhance the tribochemical reaction
between NNDM and the rubbing surface. Moreover, with the
increasing of lm depth, the contents of nitrogen and carbon
decreased, and the contents of molybdenum oxides and iron oxides
increased, it could be concluded that the long-chain alkylamidecontaining adsorption layer mainly existed on the top surface, while
the molybdenum oxides- and iron oxides-containing reaction layer
mainly existed in the inner layer. During the rubbing process, the
outer layer could protect the inner layer from being quickly rubbed
away, and then the inner reaction layer could maintain on the
rubbing surface for a longer time, thus effectively prevented the
direct contact of the surface asperities and inhibited wear and weld.
When the concentration of NNDM reached 3.0%, the contents of O,
N, Mo and carbon chains in the oil were higher than those under
other concentrations of NNDM, which was favorable to form higher
contents of long-chain alkylamide in the adsorption layers and
MoOx in the tribochemical reaction lm, as a result, the smaller
WSD and coefcient were obtained (Figs. 6 and 7), which meant
NNDM effectively decreased the friction and wear.
From Fig. 5, it seemed that the PB values of oils containing
NNDM were smaller than those of oils containing ZDDP or
MoDTC, but larger than those of base oil 150SN. It has been
known that in the EP region, the surface layer was easily erased
away and fresh metal surface exposed continuously, so under this
rigorous condition the best additive should be the one which
reacted most rapidly with the freshly exposed metal surface to
generate the most effective protective lm [38]. Especially, the
sulfur element and phosphorus element in the compounds could
react quickly with the metal surface to form S-rich or P-rich
tribolm, which was helpful to improve the extreme pressure
properties and load carrying capacity [16,31]. ZDDP which contains SP decomposes into a glassy lm containing polyphosphate,
suldes (ZnS and FeS) and oxides (Fe2O3, ZnO) of tens or hundreds
of nanometers thick to prevent wear [710]. S-containing MoDTC
could mainly form low friction MoS2 and MoOx lms to reduce
friction and wear [1114]. But it is impossible for NNDM which
does not contain SP to form tribolms with sulde or phosphate.
The tribolm NNDM-containing oil formed was mainly consisted
of long-chain alkylamide, MoOx and FeOx. Thus, the load-carrying
capacity of NNDM-containing oil was worse than those of ZDDPor MoDTC-containing oils, but better than that of base oil 150SN.
Conclusions
The main conclusions can be drawn from this research as follows:
(1) A new kind of sulfur- and phosphorus-free organomolybdenum
compound, as an effective wear-resistance and friction-reducing
additive, was successfully synthesized and characterized.
(2) When lubricated by NNDM-containing oil, friction coefcients
of the rubbing surfaces were smaller than those when
lubricated by ZDDP-containing oil under all test conditions,
and the WSDs of the surface lubricate by NNDM-containing
oil were smaller than those lubricated by ZDDP- and MoDTCcontaining oils. Especially, when the steel surface was lubricated by 150SN containing 3% NNDM, the friction coefcient
and the wear scar diameter can be decreased by 46% and 50%,
respectively, compared with that lubricated by 150SN.
(3) High amount of long-chain alkylamide and molybdenum oxides
in NNDM tribolm formed on the rubbing surface played an
important role of improving the friction-reducing and wearresistance performances.
Acknowledgments
The authors are grateful to the nancial supports of National
Natural Science Foundation of China (51005218), Fundamental
Research Funds for the Central Universities (2010ZY51, 2011YXL020).
157
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